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US5113008A - Process for producing hemiketals and hemithioketals - Google Patents

Process for producing hemiketals and hemithioketals Download PDF

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Publication number
US5113008A
US5113008A US07/643,294 US64329491A US5113008A US 5113008 A US5113008 A US 5113008A US 64329491 A US64329491 A US 64329491A US 5113008 A US5113008 A US 5113008A
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United States
Prior art keywords
mercaptan
compound
alcohol
oxetan
halogen
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Expired - Lifetime
Application number
US07/643,294
Inventor
Mark J. Pozzo
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Corteva Agriscience LLC
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Monsanto Co
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Filing date
Publication date
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Assigned to MONSANTO COMPANY, A CORP. OF DE reassignment MONSANTO COMPANY, A CORP. OF DE ASSIGNMENT OF ASSIGNORS INTEREST. Assignors: POZZO, MARK J.
Priority to US07/643,294 priority Critical patent/US5113008A/en
Priority to IL10069992A priority patent/IL100699A/en
Priority to HU9200188A priority patent/HU209982B/en
Priority to IE017492A priority patent/IE920174A1/en
Priority to DK92870014.5T priority patent/DK0496720T3/en
Priority to DE69201972T priority patent/DE69201972D1/en
Priority to KR1019920000793A priority patent/KR950004040B1/en
Priority to AU10348/92A priority patent/AU636072B2/en
Priority to JP04813392A priority patent/JP3163148B2/en
Priority to AT92870014T priority patent/ATE121068T1/en
Priority to ZA92431A priority patent/ZA92431B/en
Priority to ES92870014T priority patent/ES2072131T3/en
Priority to EP92870014A priority patent/EP0496720B1/en
Priority to CA002059728A priority patent/CA2059728A1/en
Publication of US5113008A publication Critical patent/US5113008A/en
Application granted granted Critical
Assigned to ROHM AND HAAS COMPANY reassignment ROHM AND HAAS COMPANY ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: MONSANTO COMPANY
Assigned to ROHM AND HAAS ASIA, INC. reassignment ROHM AND HAAS ASIA, INC. TRANSFER ASSIGNMENT Assignors: ROHM AND HAAS COMPANY
Assigned to DOW AGROSCIENCES LLC, A DELAWARE LIMITED LIABILITY COMPANY reassignment DOW AGROSCIENCES LLC, A DELAWARE LIMITED LIABILITY COMPANY TRANSFER ASSIGNMENT Assignors: ROHM AND HAAS ASIA, INC.
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
    • C07C45/27—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation
    • C07C45/30—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation with halogen containing compounds, e.g. hypohalogenation
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C327/00—Thiocarboxylic acids
    • C07C327/20—Esters of monothiocarboxylic acids
    • C07C327/22—Esters of monothiocarboxylic acids having carbon atoms of esterified thiocarboxyl groups bound to hydrogen atoms or to acyclic carbon atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C67/00—Preparation of carboxylic acid esters
    • C07C67/30—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group
    • C07C67/31—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group by introduction of functional groups containing oxygen only in singly bound form

Definitions

  • the present invention relates to a new and useful process for producing hemiketals and hemithioketals. More particularly, the present invention relates to a process for producing certain hemiketals and hemithioketals useful in manufacturing alkyl 4,4,4-trifluoroacetoacetate or thioalkyl 4,4,4-trifluoroacetoacetate.
  • U.K. specification No. 931,689 discloses the manufacture of fluorinated acetoacetic acid chlorides, wherein a fluorinated acetyl chloride is reacted with ketene, desirably in the presence of a suitable solvent.
  • the present invention provides a new and useful process for making hemiketals and hemithioketals.
  • the process for producing the hemiketals or hemithioketals involves bringing into reactive contact an alcohol or mercaptan and an oxetan-2-one compound having the following formula: ##STR2## wherein Hal is a halogen to produce a hemiketal or hemithioketal having the structural formula: ##STR3## where X is O or S and R is a lower alkyl, i.e., C 1 -C 12 alkyl.
  • X is O or S and R is a lower alkyl, i.e., C 1 -C 12 alkyl.
  • mercaptan is used as a reactant, it is preferred that the reaction be carried out in the presence of a catalytic amount of a tertiary amine.
  • the preferred source of the oxetan-2-one compound is a recovered by-product resulting from the manufacture of fluorinated acetoacetic acid chloride using a process, such as that disclosed in the above-mentioned U.K. specification.
  • lower alkyl and cognates thereof, such as, “alk” etc., refers to an alkyl moiety, straight or branched chain, having from 1 to about 12 carbon atoms.
  • ketene is reacted with trifluoroacetyl halide, preferably trifluoroacetyl chloride, in a solvent and at a reduced temperature to produce trifluoroacetoacetyl halide.
  • trifluoroacetyl halide preferably trifluoroacetyl chloride
  • the following equation depicts the reaction: ##STR4## wherein Hal is a halogen, such as Cl, Br or F.
  • Hal is a halogen, such as Cl, Br or F.
  • Hal is a halogen, such as Cl, Br or F.
  • the reaction mixture can be distilled to separate the Oxetan-2-one compound, solvent and trifluoroacetoacetate compound one from the other.
  • the distillation is carried out at a reduced pressure to minimize the production of unwanted by-products.
  • the oxetan-2-one compound that is recovered from the distillation operation is converted to a hemiketal or hemithioketal by reacting the same with excess lower alkyl monohydric alcohol or mercaptan, respectively.
  • the mol ratio of alcohol or mercaptan to oxetan-2-one compound is in the order of about 5:1 to 1:1.
  • a preferred ratio is 3.5:1 to 2.5:1.
  • the mixture can be heated at reflux to convert the oxetan-2-one compound into a hemiketal or hemithioketal in accordance with the following illustrative equation: ##STR6## where X, R and Hal are as defined above.
  • the resulting product is 4,4,4-trifluoro-3-ethoxy-3-hydroxy-butanoic acid, ethyl ester, where ethanol is used as a reactant or is 4,4,4-trifluoro-3-thiomethyl-3-hydroxy-butanoic acid, methylthioester where methyl mercaptan is used as a reactant.
  • the hemiketal or hemithioketal is converted to alkyl or S-alkyl trifluoroacetoacetate.
  • This can be accomplished by stripping off excess alcohol or mercaptan from the reaction mixture and, at the same time, cleaving off the alkoxy or thioalkyl radical from the hemiketal in the form of an alcohol or mercaptan.
  • the stripping and cleaving are carried out preferably at atmospheric pressure at a reflux ratio of 10:1 to 1:1, most preferably about 5:1.
  • the operation is preferably done at or near atmospheric pressure because temperatures above about 90° C. are needed to crack the hemiketal to the desired alkyl or S-alkyl 4,4,4-trifluoroacetoacetate.
  • the trifluoroacetoacetate resulting from the conversion of the hemiketal or hemithioketal can be combined with the trifluoroacetoacetate resulting from the reaction wherein the oxetan-2-one compound is produced as a by-product and thereafter used in the preparation of herbicidal pyridine compounds.
  • a product previously regarded as a waste product in the manufacturing of trifluorinated acetoacetic compounds from a fluorinated acetyl halide and ketene is converted to a product useful in preparing additional quantities of trifluoroacetoacetate, thereby increasing significantly the overall yield of trifluoroacetoacetate by about 5-10%.
  • oxetan-2-one compound to a thioate for best results should be carried out in the presence of a catalytic amount of a tertiary amine, such as triethylamine.
  • a catalytic amount may range from about 5-30% of the weight of mercaptan employed.
  • the mol ratio of oxetan-2-one compound to amine can range from about 1.5:1 to 0.5:1.
  • tertiary amines useful in the promotion of the reaction between the oxetan-2-one compound and mercaptan include trimethylamine, triethylamine, tributylamine, tri-t-butylamine, N,N-diisopropylethylamine, 4-dimethyl-aminopyridine, 1,8-diazabicyclo(5.4.0)undec-7-ene, 1,5-diazabicyclo(4.3.0)non-5-ene, 1,4-diazabicyclo(2.2.2)octane.

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  • Organic Chemistry (AREA)
  • Chemical & Material Sciences (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Agricultural Chemicals And Associated Chemicals (AREA)
  • Polyesters Or Polycarbonates (AREA)
  • Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
  • Transition And Organic Metals Composition Catalysts For Addition Polymerization (AREA)
  • Heterocyclic Carbon Compounds Containing A Hetero Ring Having Oxygen Or Sulfur (AREA)
  • Ceramic Products (AREA)
  • Nitrogen Condensed Heterocyclic Rings (AREA)
  • Plural Heterocyclic Compounds (AREA)
  • Junction Field-Effect Transistors (AREA)
  • Solid State Image Pick-Up Elements (AREA)
  • Networks Using Active Elements (AREA)
  • Compounds Of Unknown Constitution (AREA)

Abstract

Hemiketals and hemithioketals are produced by bringing into reactive contact an alcohol or mercaptan and an oxetan-2-one compound having the following structural formula: ##STR1## where Hal is a halogen.

Description

BACKGROUND OF THE INVENTION
The present invention relates to a new and useful process for producing hemiketals and hemithioketals. More particularly, the present invention relates to a process for producing certain hemiketals and hemithioketals useful in manufacturing alkyl 4,4,4-trifluoroacetoacetate or thioalkyl 4,4,4-trifluoroacetoacetate.
As part of their chemical structure, many agriculturally and pharmaceutically active compounds contain at least one trifluoromethyl functional group. The presence of one or more such groups in the compounds contributes to the desired activity of the compounds. In U.S. Pat. No. 4,785,129, compounds of alkyl 4,4,4-trifluoro-3-oxo-butanethioates, which are also referred to as thioalkyl trifluoroacetoacetates, are disclosed, along with the fact that methyl and ethyl esters of 4,4,4-trifluoro-3-oxo-butanoic acids are commercially available compounds. It is also disclosed in that patent that such compounds are useful intermediates for the preparation of herbicidal pyridine dicarbothioates and herbicidal pyridine dicarboxylates.
In U.S. Pat. No. 4,618,679, the preparation of herbicides using a 3-ketoester and suitable aldehydes as intermediates is disclosed.
Various processes for making trifluoroacetoacetic acid compounds are known. For example, U.K. specification No. 931,689 discloses the manufacture of fluorinated acetoacetic acid chlorides, wherein a fluorinated acetyl chloride is reacted with ketene, desirably in the presence of a suitable solvent.
SUMMARY OF THE INVENTION
The present invention provides a new and useful process for making hemiketals and hemithioketals.
The process for producing the hemiketals or hemithioketals involves bringing into reactive contact an alcohol or mercaptan and an oxetan-2-one compound having the following formula: ##STR2## wherein Hal is a halogen to produce a hemiketal or hemithioketal having the structural formula: ##STR3## where X is O or S and R is a lower alkyl, i.e., C1 -C12 alkyl. For best yields the mercaptan or alcohol is used in near or above stoichiometric amounts. Where mercaptan is used as a reactant, it is preferred that the reaction be carried out in the presence of a catalytic amount of a tertiary amine. The preferred source of the oxetan-2-one compound is a recovered by-product resulting from the manufacture of fluorinated acetoacetic acid chloride using a process, such as that disclosed in the above-mentioned U.K. specification.
DETAILED DESCRIPTION OF THE INVENTION
As used herein, the term "lower alkyl" and cognates thereof, such as, "alk" etc., refers to an alkyl moiety, straight or branched chain, having from 1 to about 12 carbon atoms.
In a known process, ketene is reacted with trifluoroacetyl halide, preferably trifluoroacetyl chloride, in a solvent and at a reduced temperature to produce trifluoroacetoacetyl halide. The following equation depicts the reaction: ##STR4## wherein Hal is a halogen, such as Cl, Br or F. Also, produced in substantial quantities in amounts of about 10% by weight in the reaction between ketene and a trifluoroacetyl halide is a 4-halo-4-trifluoromethyl-oxetan-2-one compound having the following structural formula: ##STR5## wherein Hal is a halogen, such as Cl, Br, or F. After quenching with either a lower alcohol or mercaptan, the reaction mixture can be distilled to separate the Oxetan-2-one compound, solvent and trifluoroacetoacetate compound one from the other. Preferably, the distillation is carried out at a reduced pressure to minimize the production of unwanted by-products.
The oxetan-2-one compound that is recovered from the distillation operation is converted to a hemiketal or hemithioketal by reacting the same with excess lower alkyl monohydric alcohol or mercaptan, respectively. For best results, the mol ratio of alcohol or mercaptan to oxetan-2-one compound is in the order of about 5:1 to 1:1. A preferred ratio is 3.5:1 to 2.5:1. The mixture can be heated at reflux to convert the oxetan-2-one compound into a hemiketal or hemithioketal in accordance with the following illustrative equation: ##STR6## where X, R and Hal are as defined above.
The resulting product is 4,4,4-trifluoro-3-ethoxy-3-hydroxy-butanoic acid, ethyl ester, where ethanol is used as a reactant or is 4,4,4-trifluoro-3-thiomethyl-3-hydroxy-butanoic acid, methylthioester where methyl mercaptan is used as a reactant.
Preferably, the hemiketal or hemithioketal is converted to alkyl or S-alkyl trifluoroacetoacetate. This can be accomplished by stripping off excess alcohol or mercaptan from the reaction mixture and, at the same time, cleaving off the alkoxy or thioalkyl radical from the hemiketal in the form of an alcohol or mercaptan. The stripping and cleaving are carried out preferably at atmospheric pressure at a reflux ratio of 10:1 to 1:1, most preferably about 5:1. The operation is preferably done at or near atmospheric pressure because temperatures above about 90° C. are needed to crack the hemiketal to the desired alkyl or S-alkyl 4,4,4-trifluoroacetoacetate. The trifluoroacetoacetate resulting from the conversion of the hemiketal or hemithioketal can be combined with the trifluoroacetoacetate resulting from the reaction wherein the oxetan-2-one compound is produced as a by-product and thereafter used in the preparation of herbicidal pyridine compounds. Thus, a product previously regarded as a waste product in the manufacturing of trifluorinated acetoacetic compounds from a fluorinated acetyl halide and ketene is converted to a product useful in preparing additional quantities of trifluoroacetoacetate, thereby increasing significantly the overall yield of trifluoroacetoacetate by about 5-10%.
It has been found that the conversion of oxetan-2-one compound to a thioate for best results should be carried out in the presence of a catalytic amount of a tertiary amine, such as triethylamine. A catalytic amount may range from about 5-30% of the weight of mercaptan employed. The mol ratio of oxetan-2-one compound to amine can range from about 1.5:1 to 0.5:1. Examples of tertiary amines useful in the promotion of the reaction between the oxetan-2-one compound and mercaptan include trimethylamine, triethylamine, tributylamine, tri-t-butylamine, N,N-diisopropylethylamine, 4-dimethyl-aminopyridine, 1,8-diazabicyclo(5.4.0)undec-7-ene, 1,5-diazabicyclo(4.3.0)non-5-ene, 1,4-diazabicyclo(2.2.2)octane.
The following examples are given to more particularly illustrate the invention and the invention is not to be regarded as being limited thereto. All parts are given on a weight basis unless otherwise indicated.
EXAMPLE 1
Three parts of absolute ethanol and 1 part of 4-chloro-4-trifluoromethyl-oxetan-2-one contained in the low boiling distillate of the reaction product of ketene and fluorinated acetoacetic acid chloride were mixed together and heated at reflux at a temperature of about 100° C. for one hour. It was determined that the reaction product comprised about 40% by weight 4,4,4-trifluoro3-ethoxy-3-hydroxy-butanoic acid, ethyl ester.
EXAMPLE 2
Three parts of methyl mercaptan, 1 part of 4-chloro-4-trifluoromethyl-oxetan-2-one contained in the low boiling distillate of the reaction product of ketene and fluorinated acetoacetic acid chloride, and 0.2 part of triethylamine were heated at reflux at a temperature of about 100° C. for one hour. It was determined that the reaction product comprised about 40% by weight 4,4,4-trifluoro-3-ethoxy-3-hydroxy-butanoic acid, methylthioate.
While the illustrative embodiments of the invention have been described with particularity, it will be understood that various other modifications will be apparent to and can be readily made by those skilled in the art without departing from the spirit and scope of the invention. Accordingly, it is not intended that the scope of the claims appended hereto be limited to the examples and description set forth hereinabove but rather that the claims be construed as encompassing all the features of patentable novelty which reside in the present invention, including all features which would be treated as equivalents thereof by those skilled in the art to which the invention pertains.

Claims (18)

What is claimed is:
1. A process for producing a hemiketal comprising bringing into reactive contact an oxetan-2-one compound having the formula: ##STR7## wherein Hal is a halogen with an alcohol to produce a hemiketal having the formula: ##STR8## wherein R is a lower alkyl radical.
2. The process of claim 1 wherein the alcohol is present in near or above stoichiometric amount.
3. The process of claim 2 wherein the alcohol and oxetane-2-one compound are heated at reflux to produce the hemiketal.
4. The process of claim 2 wherein the mol ratio of alcohol to oxetane-2-one compound is in the order of about 5:1 to 1.5:1.
5. The process of claim 3 wherein the mol ratio is from 3.5:1 to 2.5:1.
6. The process of claim 1 wherein the alcohol is ethanol.
7. The process of claim 2 wherein the alcohol is ethanol.
8. The process of claim 3 wherein the alcohol is ethanol.
9. A process for producing a hemithioketal comprising bringing into reactive contact in the presence of a catalytic amount of a tertiary amine an oxetan-2-one compound having the formula: ##STR9## wherein Hal is a halogen with a mercaptan to produce a hemithioketal having the formula: ##STR10## wherein R is a lower alkyl radical.
10. The process of claim 9 wherein the mercaptan is present in near or above stoichiometric amount.
11. The process of claim 10 wherein the mercaptan and oxetan-2-one compound are heated at reflux to produce the hemithioketal.
12. The process of claim 9 wherein the mol ratio of mercaptan to oxetan-2-one compound is in the order of about 5:1 to 1.5:1.
13. The process of claim 2 wherein the mol ratio of mercaptan to oxetane-2-one compound is in the order of about 3.5:1 to 2.5:1.
14. The process of claim 9 wherein the mercaptan is methyl mercaptan.
15. The process of claim 10 wherein the mercaptan is methyl mercaptan.
16. The process of claim 11 wherein the mercaptan is methyl mercaptan.
17. The process of claim 1 wherein the halogen is chlorine.
18. The process of claim 9 wherein the halogen is chlorine.
US07/643,294 1991-01-22 1991-01-22 Process for producing hemiketals and hemithioketals Expired - Lifetime US5113008A (en)

Priority Applications (14)

Application Number Priority Date Filing Date Title
US07/643,294 US5113008A (en) 1991-01-22 1991-01-22 Process for producing hemiketals and hemithioketals
IL10069992A IL100699A (en) 1991-01-22 1992-01-19 Process for producing hemiketals and hemithioketals
JP04813392A JP3163148B2 (en) 1991-01-22 1992-01-21 Method for producing hemiketal and hemithioketal
ES92870014T ES2072131T3 (en) 1991-01-22 1992-01-21 PROCEDURE FOR THE PRODUCTION OF HEMICETALS AND HEMITIOCETALS.
DK92870014.5T DK0496720T3 (en) 1991-01-22 1992-01-21 Process for the preparation of hemiketals and hemithioketals
DE69201972T DE69201972D1 (en) 1991-01-22 1992-01-21 Methods of making hemiketals and hemithioketals.
KR1019920000793A KR950004040B1 (en) 1991-01-22 1992-01-21 Process for producing hemiketals and hemithioketals
AU10348/92A AU636072B2 (en) 1991-01-22 1992-01-21 Process for producing hemiketals and hemithioketals
HU9200188A HU209982B (en) 1991-01-22 1992-01-21 Process for producing hemiketals and hemithioketals
AT92870014T ATE121068T1 (en) 1991-01-22 1992-01-21 METHOD FOR PRODUCING HEMIKETALS AND HEMITHIOKETALS.
ZA92431A ZA92431B (en) 1991-01-22 1992-01-21 Process for producing hemiketals and hemithioketals.
IE017492A IE920174A1 (en) 1991-01-22 1992-01-21 Process for producing hemiketals and hemithioketals
EP92870014A EP0496720B1 (en) 1991-01-22 1992-01-21 Process for producing hemiketals and hemithioketals
CA002059728A CA2059728A1 (en) 1991-01-22 1992-01-21 Process for producing hemiketals and hemithioketals

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US07/643,294 US5113008A (en) 1991-01-22 1991-01-22 Process for producing hemiketals and hemithioketals

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US5113008A true US5113008A (en) 1992-05-12

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US07/643,294 Expired - Lifetime US5113008A (en) 1991-01-22 1991-01-22 Process for producing hemiketals and hemithioketals

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EP (1) EP0496720B1 (en)
JP (1) JP3163148B2 (en)
KR (1) KR950004040B1 (en)
AT (1) ATE121068T1 (en)
AU (1) AU636072B2 (en)
CA (1) CA2059728A1 (en)
DE (1) DE69201972D1 (en)
DK (1) DK0496720T3 (en)
ES (1) ES2072131T3 (en)
HU (1) HU209982B (en)
IE (1) IE920174A1 (en)
IL (1) IL100699A (en)
ZA (1) ZA92431B (en)

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US8575273B2 (en) 2008-11-26 2013-11-05 Schlumberger Technology Corporation Coupling agents and compositions produced using them
US9403962B2 (en) 2011-12-22 2016-08-02 Schlumberger Technology Corporation Elastomer compositions with silane functionalized silica as reinforcing fillers

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB931689A (en) * 1960-12-17 1963-07-17 Hoechst Ag Process for the manufacture of fluorinated acetoacetic acid chlorides and the solutions thereof
US4618679A (en) * 1983-08-11 1986-10-21 Monsanto Company 3,5-dicarboxylic acid esters of 2,6-bis(fluoro-alkyl)-2,6-bis(hydroxy) piperidines
US4647689A (en) * 1982-07-30 1987-03-03 Monsanto Company Preparation of alkyl trifluoroacetoacetate
US4785129A (en) * 1988-02-16 1988-11-15 Monsanto Company Methyl 4,4,4-trifluoro-3-oxo-butanethioate

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB931689A (en) * 1960-12-17 1963-07-17 Hoechst Ag Process for the manufacture of fluorinated acetoacetic acid chlorides and the solutions thereof
US4647689A (en) * 1982-07-30 1987-03-03 Monsanto Company Preparation of alkyl trifluoroacetoacetate
US4618679A (en) * 1983-08-11 1986-10-21 Monsanto Company 3,5-dicarboxylic acid esters of 2,6-bis(fluoro-alkyl)-2,6-bis(hydroxy) piperidines
US4785129A (en) * 1988-02-16 1988-11-15 Monsanto Company Methyl 4,4,4-trifluoro-3-oxo-butanethioate

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CA2059728A1 (en) 1992-07-23
HU209982B (en) 1995-01-30
IL100699A (en) 1996-09-12
AU1034892A (en) 1992-07-30
JPH04321645A (en) 1992-11-11
EP0496720A1 (en) 1992-07-29
ATE121068T1 (en) 1995-04-15
ZA92431B (en) 1993-03-08
HUT60990A (en) 1992-11-30
JP3163148B2 (en) 2001-05-08
KR920014752A (en) 1992-08-25
ES2072131T3 (en) 1995-07-01
AU636072B2 (en) 1993-04-08
IE920174A1 (en) 1992-07-29
KR950004040B1 (en) 1995-04-22
IL100699A0 (en) 1992-09-06
DK0496720T3 (en) 1995-07-31
DE69201972D1 (en) 1995-05-18
HU9200188D0 (en) 1992-05-28
EP0496720B1 (en) 1995-04-12

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